JP2023514922A - Fluorescent quantum dots and their preparation method and uses - Google Patents
Fluorescent quantum dots and their preparation method and uses Download PDFInfo
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- JP2023514922A JP2023514922A JP2022536547A JP2022536547A JP2023514922A JP 2023514922 A JP2023514922 A JP 2023514922A JP 2022536547 A JP2022536547 A JP 2022536547A JP 2022536547 A JP2022536547 A JP 2022536547A JP 2023514922 A JP2023514922 A JP 2023514922A
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- silver
- source
- quantum dots
- gold
- selenium
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 201
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 229910052709 silver Inorganic materials 0.000 claims abstract description 56
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002798 polar solvent Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 150000001450 anions Chemical class 0.000 claims abstract description 20
- 150000001768 cations Chemical class 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 10
- 238000012984 biological imaging Methods 0.000 claims abstract description 9
- IANXFCFDMBNAHB-UHFFFAOYSA-N gold selanylidenesilver Chemical compound [Au].[Ag]=[Se] IANXFCFDMBNAHB-UHFFFAOYSA-N 0.000 claims description 55
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 41
- KDSXXMBJKHQCAA-UHFFFAOYSA-N disilver;selenium(2-) Chemical compound [Se-2].[Ag+].[Ag+] KDSXXMBJKHQCAA-UHFFFAOYSA-N 0.000 claims description 41
- 239000011669 selenium Substances 0.000 claims description 40
- 229910052711 selenium Inorganic materials 0.000 claims description 31
- 229940091258 selenium supplement Drugs 0.000 claims description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052737 gold Inorganic materials 0.000 claims description 30
- 239000010931 gold Substances 0.000 claims description 30
- 229910052946 acanthite Inorganic materials 0.000 claims description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 20
- 229940056910 silver sulfide Drugs 0.000 claims description 19
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 14
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 13
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 12
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- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 8
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- 229910002688 Ag2Te Inorganic materials 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 8
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 8
- 229940045105 silver iodide Drugs 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 8
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 claims description 7
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 7
- YRXWPCFZBSHSAU-UHFFFAOYSA-N [Ag].[Ag].[Te] Chemical compound [Ag].[Ag].[Te] YRXWPCFZBSHSAU-UHFFFAOYSA-N 0.000 claims description 7
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 claims description 7
- YWWZCHLUQSHMCL-UHFFFAOYSA-N diphenyl diselenide Chemical compound C=1C=CC=CC=1[Se][Se]C1=CC=CC=C1 YWWZCHLUQSHMCL-UHFFFAOYSA-N 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 229910001922 gold oxide Inorganic materials 0.000 claims description 7
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 claims description 7
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims description 7
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims description 7
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 octanethio Chemical compound 0.000 claims description 7
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 7
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 7
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 7
- NSVHDIYWJVLAGH-UHFFFAOYSA-M silver;n,n-diethylcarbamodithioate Chemical compound [Ag+].CCN(CC)C([S-])=S NSVHDIYWJVLAGH-UHFFFAOYSA-M 0.000 claims description 7
- 229960001881 sodium selenate Drugs 0.000 claims description 7
- 239000011655 sodium selenate Substances 0.000 claims description 7
- 235000018716 sodium selenate Nutrition 0.000 claims description 7
- VPQBLCVGUWPDHV-UHFFFAOYSA-N sodium selenide Chemical compound [Na+].[Na+].[Se-2] VPQBLCVGUWPDHV-UHFFFAOYSA-N 0.000 claims description 7
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940071536 silver acetate Drugs 0.000 claims description 6
- 229960001471 sodium selenite Drugs 0.000 claims description 6
- 239000011781 sodium selenite Substances 0.000 claims description 6
- 235000015921 sodium selenite Nutrition 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
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- 229910052763 palladium Inorganic materials 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
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- DJKHDIWPSBMISY-UHFFFAOYSA-N [Na].[TeH2] Chemical compound [Na].[TeH2] DJKHDIWPSBMISY-UHFFFAOYSA-N 0.000 claims description 3
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
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- 229940056932 lead sulfide Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VCEXCCILEWFFBG-UHFFFAOYSA-N mercury telluride Chemical compound [Hg]=[Te] VCEXCCILEWFFBG-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000019155 Radiation injury Diseases 0.000 description 1
- HXVARUKJZTVIIN-UHFFFAOYSA-N [Se].[Fe].[Ag] Chemical compound [Se].[Fe].[Ag] HXVARUKJZTVIIN-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 201000011510 cancer Diseases 0.000 description 1
- XPLGYTMJAYEMAT-UHFFFAOYSA-N copper;sulfanylidenesilver Chemical compound [Ag].[Cu]=S XPLGYTMJAYEMAT-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- WQIJNCUKAOHNPM-UHFFFAOYSA-L silver selenite Chemical compound [Ag+].[Ag+].[O-][Se]([O-])=O WQIJNCUKAOHNPM-UHFFFAOYSA-L 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
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Abstract
本出願は、蛍光量子ドットおよびその調製方法並びに用途を開示する。前記調製方法は、銀源、陰イオン源、弱極性溶媒を含む第１の均一混合反応体系を溶媒熱反応させて、銀系量子ドット前駆体を調製するステップと、銀系量子ドット前駆体、陰イオン源および／または金属陽イオン源を含む第２の均一混合反応体系をイオン交換反応させて、合金化蛍光量子ドットを取得し、その蛍光発光ピーク波長が５００～１７００ｎｍで、絶対量子効率が８５％を超えるステップとを含む。本出願はまず簡単な高温ソルボサーマル法によって銀系量子ドットを調製し、次にイオン交換法によって合金化量子ドットを取得し、その合成プロセスが簡単で制御しやすく、収率が高く、大規模に調製可能であり、蛍光発光が可視光から近赤外線までにあり調整可能であり、優れた光安定性を有し、同時に有毒な重金属元素を含まないため、生物学的画像化、近赤外線デバイスなどの分野において幅広い用途の見通しを持っている。【選択図】図１The present application discloses fluorescent quantum dots and their preparation methods and uses. The preparation method comprises a step of solvent-thermally reacting a first homogeneous mixed reaction system comprising a silver source, an anion source, and a weakly polar solvent to prepare a silver-based quantum dot precursor; A second homogeneous mixed reaction system containing an anion source and/or a metal cation source is subjected to an ion exchange reaction to obtain alloyed fluorescent quantum dots, which have a fluorescence emission peak wavelength of 500-1700 nm and an absolute quantum efficiency of greater than 85%. This application first prepares silver-based quantum dots by a simple high-temperature solvothermal method, and then obtains alloyed quantum dots by an ion-exchange method, whose synthesis process is simple, easy to control, high yield, and large-scale. , tunable fluorescence emission from visible to near-infrared, excellent photostability, and free of toxic heavy metal elements, making it suitable for biological imaging, near-infrared devices It has wide application prospects in fields such as [Selection drawing] Fig. 1
Description
（関連出願）
本出願は、２０２１年１月２０日に出願された中国出願番号２０２１１００７３２３０．０号、発明名称「近赤外線銀金セレン蛍光量子ドットおよびその調製方法並びに用途」、および２０２１年１０月２５日に出願された中国出願番号２０２１１１２４３９５９．４号、発明名称「合金化蛍光量子ドットおよびその調製方法並びに用途」という２つの中国特許出願の優先権を主張する。
(Related application)
The present application is Chinese Application No. 202110073230.0, filed on January 20, 2021, entitled "Near-infrared silver-gold-selenium fluorescent quantum dots and their preparation method and application", and filed on October 25, 2021. No. 202111243959.4 filed in China claims priority from two Chinese patent applications entitled "Alloyed Fluorescent Quantum Dots and Preparation Methods and Uses Thereof".
（技術分野）
本出願は、蛍光量子ドットおよびその調製方法に関し、特に合金化蛍光量子ドットおよびその調製方法、高量子効率を有する近赤外線銀金セレン蛍光量子ドットおよびその調製方法並びに用途に関し、材料科学技術の分野に属する。
(Technical field)
The present application relates to fluorescent quantum dots and their preparation methods, especially alloyed fluorescent quantum dots and their preparation methods, near-infrared silver gold selenium fluorescent quantum dots with high quantum efficiency and their preparation methods and applications, in the field of materials science and technology. belongs to
蛍光イメージング技術には、非接触で直感的な画像、リアルタイム、高感度、経済的で便利、そして放射線障害がないという利点があり、生物医学研究および臨床診療において、特に蛍光イメージングの外科的ナビゲーションにおいて、幅広い応用の見通しを持っている。蛍光イメージングの波長範囲によると、主に可視光蛍光イメージング（４００-６５０ｎｍ）と近赤外蛍光イメージング（６５０-１７００ｎｍ）が含まれる。生物学的イメージングでは、近赤外光を、近赤外線Ｉ区（６５０-９００ｎｍ、ＮＩＲ－Ｉ）と近赤外線（９００-１７００ｎｍ、ＮＩＲ－ＩＩ）という２つの光学ウィンドウに分割できる。ＮＩＲ蛍光は、過去１０年間のインビボ蛍光イメージング研究で発見された新しい蛍光ウィンドウであり、可視領域およびＮＩＲ－Ｉ領域と比較して、生体組織内のＮＩＲ－ＩＩ光子の減衰係数が大幅に低減する（Ｊ． Ａｍ． Ｃｈｅｍ． Ｓｏｃ． ２０２０, １４２, １４７８９-１４８０４．）、したがって、ＮＩＲ－ＩＩ蛍光は、インビボイメージングでより高い組織侵入深さと空間分解能を備えている。 Fluorescence imaging techniques have the advantages of non-contact, intuitive imaging, real-time, high sensitivity, economical convenience, and no radiation injury, and are widely used in biomedical research and clinical practice, especially in surgical navigation of fluorescence imaging. , has broad application prospects. According to the wavelength range of fluorescence imaging, it mainly includes visible light fluorescence imaging (400-650 nm) and near-infrared fluorescence imaging (650-1700 nm). In biological imaging, near-infrared light can be split into two optical windows: near-infrared I (650-900 nm, NIR-I) and near-infrared (900-1700 nm, NIR-II). NIR fluorescence is a new fluorescence window discovered in the last decade of in vivo fluorescence imaging studies, which significantly reduces the extinction coefficient of NIR-II photons in living tissue compared to the visible and NIR-I regions. (J. Am. Chem. Soc. 2020, 142, 14789-14804.) Therefore, NIR-II fluorescence has higher tissue penetration depth and spatial resolution for in vivo imaging.
優れた蛍光発光材料として、量子ドットは、高い生体適合性、高い量子効率、調整可能な励起および発光波長、および容易な表面機能化などの特徴を備え、インビボイメージング、発光ダイオード、光検出器、レーザー、太陽電池などに幅広い用途がある。しかしながら、硫化鉛、テルル化カドミウム、セレン化鉛、テルル化水銀、セレン化銀などの既存の蛍光量子ドットは、絶対蛍光量子収率が低いか、一部に有毒な重金属元素が含まれており、蛍光強度と毒性の両立が困難である。したがって、可視から近赤外のフルウィンドウ（５００-１７００ｎｍ）で、連続的に調整可能な単一発光、高い蛍光量子効率、および高い生体適合性を備えた新しい蛍光量子ドット材料を開発することが急務である。 As excellent fluorescent light-emitting materials, quantum dots possess features such as high biocompatibility, high quantum efficiency, tunable excitation and emission wavelengths, and easy surface functionalization, making them ideal for in vivo imaging, light-emitting diodes, photodetectors, It has a wide range of applications, such as lasers and solar cells. However, existing fluorescent quantum dots such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, and silver selenide have low absolute fluorescence quantum yields, or some contain toxic heavy metal elements. , it is difficult to achieve both fluorescence intensity and toxicity. Therefore, it is possible to develop novel fluorescent quantum dot materials with continuously tunable single emission, high fluorescence quantum efficiency and high biocompatibility in the full visible to near-infrared window (500-1700 nm). It is urgent.
本出願の主な目的は、従来の量子ドット特性の欠陥を克服するための高量子効率の蛍光量子ドットおよびその調製方法並びに用途を提供することである。 The main objective of the present application is to provide high quantum efficiency fluorescent quantum dots and their preparation methods and applications to overcome the deficiencies of conventional quantum dot properties.
前記の発明目的を達成するために、本出願は以下の技術的解決策を提供する。 In order to achieve the above invention objectives, the present application provides the following technical solutions.
本出願の実施例は、合金化蛍光量子ドットの調製方法を提供し、この方法は、
銀源、陰イオン源、弱極性溶媒を含む第１の均一混合反応体系を溶媒熱反応させ、銀系量子ドット前駆体を調製するステップと、
銀系量子ドット前駆体、陰イオン源および／または金属陽イオン源を含む第２の均一混合反応体系を０～２６０℃で０．４～７２時間イオン交換反応させて、合金化蛍光量子ドットを取得するステップと、を含む。
Examples of the present application provide a method of preparing alloyed fluorescent quantum dots, the method comprising:
solvothermally reacting a first homogeneous mixed reaction system comprising a silver source, an anion source, and a weakly polar solvent to prepare a silver-based quantum dot precursor;
A second homogeneous mixed reaction system comprising a silver-based quantum dot precursor, an anion source and/or a metal cation source is subjected to an ion exchange reaction at 0-260° C. for 0.4-72 hours to form alloyed fluorescent quantum dots. and obtaining.
いくつかの実施例では、前記陰イオン源は硫黄源、セレン源およびテルル源のいずれか１つまたは２つ以上の組み合わせを含む。 In some embodiments, the anion source includes any one or a combination of two or more of a sulfur source, a selenium source and a tellurium source.
いくつかの実施例では、前記金属陽イオン源に含まれる金属元素は、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｕ、Ｐｄ、Ｐｔ、Ｉｎのいずれか１つまたは２つ以上の組み合わせを含む。 In some embodiments, the metal element contained in the metal cation source is any one or a combination of two or more of Mn, Fe, Co, Ni, Cu, Zn, Au, Pd, Pt, and In. include.
本出願の実施例は、前記方法によって調製された合金化蛍光量子ドットをさらに提供し、その蛍光発光ピーク波長が５００～１７００ｎｍである。 Examples of the present application further provide alloyed fluorescent quantum dots prepared by the above method, which have a fluorescence emission peak wavelength of 500-1700 nm.
さらに、前記合金化蛍光量子ドットの絶対量子効率が８５％を超える。 Furthermore, the absolute quantum efficiency of said alloyed fluorescent quantum dots exceeds 85%.
さらに、前記合金化蛍光量子ドットは、ＡｇＡｕＳｅ、ＡｇＡｕＳ、ＡｇＡｕＴｅ、ＣｕＡｇＳ、ＣｕＡｇＳｅ、ＡｇＩｎＴｅ２のいずれか１つまたは２つ以上の組み合わせを含む。 Further, the alloyed fluorescent quantum dots include any one or a combination of two or more of AgAuSe, AgAuS, AgAuTe, CuAgS, CuAgSe, AgInTe2 .
さらに、前記合金化蛍光量子ドットはドープされた合金化蛍光量子ドットを含む。 Further, the alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots.
さらに、前記合金化蛍光量子ドットはコアシェル構造を有する。 Furthermore, the alloyed fluorescent quantum dots have a core-shell structure.
本出願の実施例は、近赤外線銀金セレン蛍光量子ドットの調製方法をさらに提供し、この方法は、
銀源、セレン源、弱極性溶媒を含む第３の均一混合反応体系を溶媒熱反応させ、セレン化銀量子ドット前駆体を調製するステップと、
セレン化銀量子ドット前駆体、金源を含む第４の均一混合反応体系を０～２００℃で１０～７２時間陽イオン交換反応させて、近赤外線銀金セレン蛍光量子ドットを取得するステップと、を含む。
Examples of the present application further provide a method for preparing near-infrared silver gold selenium fluorescent quantum dots, the method comprising:
Solvothermally reacting a third homogeneous mixed reaction system comprising a silver source, a selenium source, and a weakly polar solvent to prepare a silver selenide quantum dot precursor;
a fourth homogeneous mixed reaction system comprising a silver selenide quantum dot precursor and a gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots; including.
本出願の実施例は、前記方法によって調製された近赤外線銀金セレン蛍光量子ドットをさらに提供し、前記近赤外線銀金セレン蛍光量子ドットの直径は２～２０ｎｍであり、サイズ分布が均一であり、その蛍光発光ピーク波長が８００～１７００ｎｍであり、絶対蛍光量子収率が９０％を超える。 Examples of the present application further provide near-infrared silver gold selenium fluorescent quantum dots prepared by the method, wherein the near infrared silver gold selenium fluorescent quantum dots have a diameter of 2-20 nm and a uniform size distribution. , its fluorescence emission peak wavelength is between 800 and 1700 nm, and the absolute fluorescence quantum yield exceeds 90%.
本出願の実施例は、生物学的画像化、生物医学または近赤外線デバイス（例えば近赤外線発光ダイオード、太陽電池、光検出器、レーザー）などの分野における、前記の合金化蛍光量子ドットまたは近赤外線銀金セレン蛍光量子ドットの用途をさらに提供する。 Examples of the present application are the alloyed fluorescent quantum dots or near-infrared Further provided are uses of the silver gold selenium fluorescent quantum dots.
従来技術と比較すると、本出願は以下の有益な効果を有する。 Compared with the prior art, the present application has the following beneficial effects.
１）本出願はまず簡単な高温ソルボサーマル法によって銀系量子ドット（セレン化銀量子ドットを含む）を調製し、次にイオン交換法によって合金化量子ドットを取得し、その合成プロセスステップが簡単で、実験条件を制御しやすく、使用される試薬は簡単に入手でき、最終生成物の収率が高く、大規模生産に適している。 1) The present application first prepares silver-based quantum dots (including silver-selenide quantum dots) by a simple high-temperature solvothermal method, and then obtains alloyed quantum dots by an ion-exchange method, and its synthesis process steps are simple. , the experimental conditions are easy to control, the reagents used are readily available, the yield of the final product is high, and it is suitable for large-scale production.
２）本出願で調製された最終生成物である合金化蛍光量子ドットは、サイズ分布が均一で、蛍光発光が可視光から近赤外線まで調整可能であり、優れた光安定性を有すると同時に、有毒な重金属元素を含まないため、生物学的画像化、近赤外線デバイスなどの分野で幅広い用途の見通しを持っている。 2) the final product alloyed fluorescent quantum dots prepared in this application have a uniform size distribution, tunable fluorescence emission from visible to near-infrared light, and excellent photostability, while at the same time; Since it does not contain toxic heavy metal elements, it has broad application prospects in the fields of biological imaging, near-infrared devices, etc.
３）本出願の調製プロセスは、他の蛍光量子ドットの調製プロセスにも適用され得、収率が高く、反応規模を拡大することが容易である。 3) The preparation process of the present application can also be applied to the preparation process of other fluorescent quantum dots, with high yield and easy scale-up of the reaction.
本出願の技術的解決策をより明確に説明するために、以下、実施例または従来技術の説明において使用される必要のある図面を簡単に説明するが、以下説明される図面は本発明のいくつかの実施例に過ぎず、当業者は、創造的な労働をすることなく、これらの図面に基づいて他の図面を得ることができるのは明らかである。 In order to describe the technical solutions of the present application more clearly, the following briefly describes the drawings that need to be used in the examples or the description of the prior art. It is obvious that these are only examples and those skilled in the art can derive other drawings based on these drawings without creative effort.
上記のように、例えば硫化鉛、テルル化カドミウム、セレン化鉛、テルル化水銀、セレン化銀などの従来の蛍光量子ドットは、その絶対蛍光量子収率が高くない同時に一部が有毒な重金属元素を含み、蛍光強度と毒性の両立が困難である。長期にわたる研究と多くの実践の結果、本件の発明者は、いくつかの元素と銀ベースの量子ドットとの間のイオン交換によって得られた合金化量子ドットが良好な光学特性を有することを発見した。以下、本出願の技術的解決策をより詳細に解釈および説明する。 As mentioned above, conventional fluorescent quantum dots, such as lead sulfide, cadmium telluride, lead selenide, mercury telluride, silver selenide, etc., do not have high absolute fluorescence quantum yield, while some of them are toxic heavy metal elements. It is difficult to achieve both fluorescence intensity and toxicity. After a long period of research and many practices, the present inventor found that alloyed quantum dots obtained by ion exchange between some elements and silver-based quantum dots have good optical properties. bottom. The technical solutions of the present application are interpreted and described in more detail below.
本出願の技術的解決策の一側面として、かかる合金化蛍光量子ドットの調製方法は、
銀源、陰イオン源、弱極性溶媒を含む第１の均一混合反応体系を溶媒熱反応させ、銀系量子ドット前駆体を調製するステップと、
銀系量子ドット前駆体、陰イオン源および／または金属陽イオン源を含む第２の均一混合反応体系を０～２６０℃で０．４～７２時間イオン交換反応させて、合金化蛍光量子ドットを取得するステップと、を含む。
As one aspect of the technical solution of the present application, the method for preparing such alloyed fluorescent quantum dots includes:
solvothermally reacting a first homogeneous mixed reaction system comprising a silver source, an anion source, and a weakly polar solvent to prepare a silver-based quantum dot precursor;
A second homogeneous mixed reaction system comprising a silver-based quantum dot precursor, an anion source and/or a metal cation source is subjected to an ion exchange reaction at 0-260° C. for 0.4-72 hours to form alloyed fluorescent quantum dots. and obtaining.
いくつかの実施形態では、前記銀源は銀塩、前記銀塩包括塩化銀、臭化銀、ヨウ化銀、硫酸銀、硝酸銀、炭酸銀、酢酸銀、硫化銀、トリフルオロ酢酸銀、ジエチルジチオカルバミン酸銀などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, said silver source is a silver salt, said silver salt entrained silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver acetate, silver sulfide, silver trifluoroacetate, diethyldithiocarbamine including, but not limited to, any one or a combination of two or more, such as silver oxide;
いくつかの実施形態では、前記陰イオン源は硫黄源、セレン源およびテルル源などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, the anion source includes any one or a combination of two or more of, but not limited to, a sulfur source, a selenium source, and a tellurium source.
さらに、前記硫黄源は硫黄、チオ硫酸ナトリウム、硫化ナトリウム、チオ尿素などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Additionally, the sulfur source includes, but is not limited to, any one or a combination of two or more of sulfur, sodium thiosulfate, sodium sulfide, thiourea, and the like.
さらに、前記セレン源は二酸化セレン、セレン、セレン酸ナトリウム、亜セレン酸ナトリウム、セレン化ナトリウム、ジフェニルジセレニドなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, the selenium source includes, but is not limited to, any one or a combination of two or more of selenium dioxide, selenium, sodium selenate, sodium selenite, sodium selenide, diphenyldiselenide, and the like.
さらに、前記テルル源はテルル、テルル酸ナトリウム、水素化テルルナトリウムなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, the tellurium source includes, but is not limited to, any one or a combination of two or more of tellurium, sodium tellurate, sodium tellurium hydride, and the like.
さらに、前記弱極性溶媒はオレイルアミン、オレイン酸、オクタデセン、オクタデシルアミン、ドデシルアミン、テトラデシルアミン、ドデカンチオール、オクタンチオ、オクタデカンチオールなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, the weakly polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethio, octadecanethiol, etc., but is limited thereto. not.
いくつかの実施形態では、前記銀源と陰イオン源の質量比は１～１０：１～１０である。 In some embodiments, the silver source to anion source weight ratio is 1-10:1-10.
いくつかの実施形態では、前記溶媒熱反応の温度は１００～３００℃で、時間は０．５～２４時間である。 In some embodiments, the temperature of said solvothermal reaction is 100-300° C. and the time is 0.5-24 hours.
いくつかの好ましい実施形態では、前記銀系量子ドット前駆体はＡｇ２Ｓ、Ａｇ２Ｓｅ、Ａｇ２Ｔｅなどのいずれか１つまたは２つ以上の組み合わせであり得るが、これらに限定されない。 In some preferred embodiments, the silver-based quantum dot precursor may be any one or a combination of two or more of Ag 2 S, Ag 2 Se, Ag 2 Te, etc., but not limited thereto.
さらに、より典型的な実施例では、前記調製方法は、まず硝酸銀をオレイルアミンに溶解し、硫黄源を加えて、２００℃で１～６時間反応させた後洗浄して、標的生成物である銀系量子ドット前駆体を取得するステップを含み得る。 Further, in a more typical embodiment, the preparation method comprises first dissolving silver nitrate in oleylamine, adding a sulfur source, reacting at 200° C. for 1-6 hours, and then washing to obtain the target product silver. obtaining a system quantum dot precursor.
いくつかのより好ましい実施形態では、前記調製方法は、質量０．１～１ｇの銀塩を取って弱極性溶媒に溶解するステップを含み得る。 In some more preferred embodiments, the preparation method may comprise taking a silver salt with a mass of 0.1-1 g and dissolving it in a weakly polar solvent.
さらに、前記調製方法は、具体的に、前記硫化銀前駆体と金源を混合し、１００℃で反応させて、銀金硫黄蛍光量子ドットを取得するステップを含む。 Further, the preparation method specifically includes the step of mixing the silver sulfide precursor and the gold source and reacting at 100° C. to obtain silver-gold-sulfur fluorescent quantum dots.
さらに、前記調製方法は、反応が完了した後、得られた銀金硫黄蛍光量子ドットを洗浄するステップをさらに含み得る。 Moreover, the preparation method may further comprise washing the obtained silver-gold-sulfur fluorescent quantum dots after the reaction is completed.
いくつかの実施形態では、前記銀系量子ドット前駆体と金属陽イオン源の質量比は１～１０：１～１０である。 In some embodiments, the weight ratio of the silver-based quantum dot precursor to the metal cation source is 1-10:1-10.
いくつかの好ましい実施形態では、前記金属陽イオン源に含まれる金属元素は、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｕ、Ｐｄ、Ｐｔ、Ｉｎなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some preferred embodiments, the metal element contained in the metal cation source is any one or more of Mn, Fe, Co, Ni, Cu, Zn, Au, Pd, Pt, In and the like. Including but not limited to combinations.
さらに、前記金属陽イオン源は、塩化第二鉄、塩化第一鉄、硫酸第二鉄、硫酸第一鉄、硝酸鉄、塩化コバルト、硝酸コバルト、硫酸コバルト、酢酸コバルト、塩化ニッケル、硝酸ニッケル、硫酸ニッケル、酢酸ニッケル、硫酸銅、酢酸銅、硝酸銅、塩化第二銅、塩化第一銅、酢酸亜鉛、硝酸亜鉛、硫酸亜鉛、塩化亜鉛、クロロ金酸ナトリウム、クロロ金酸、硝酸金、塩化金、水酸化金、酸化金、酢酸パラジウム、硝酸パラジウム、塩化パラジウム、クロロ白金酸、クロロ白金酸ナトリウム、クロロ白金酸カリウム、酢酸インジウム、塩化インジウムなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, the source of metal cations is ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, iron nitrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, Nickel sulfate, nickel acetate, copper sulfate, copper acetate, copper nitrate, cupric chloride, cuprous chloride, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium chloroaurate, chloroauric acid, gold nitrate, chloride Any one or a combination of two or more of gold, gold hydroxide, gold oxide, palladium acetate, palladium nitrate, palladium chloride, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, indium acetate, indium chloride, etc. Including but not limited to.
その中で、前記銀塩、陰イオン源、弱極性溶媒と金属陽イオン源などは上記のものから選択できるが、それらに限定されない。 Among them, the silver salt, anion source, weakly polar solvent and metal cation source, etc. can be selected from the above, but are not limited thereto.
いくつかの実施形態では、前記調製方法は具体的に、
銀源と弱極性溶媒を均一に混合し陰イオン源を加え、溶媒熱反応を行って、銀系量子ドット前駆体（「銀ベース量子ドット前駆体」とも呼ばれる）を取得するステップと、
前記銀系量子ドット前駆体と金属陽イオン源を０～２６０℃で混合し反応させて、合金化蛍光量子ドットを得、その蛍光発光ピーク波長が５００～１７００ｎｍであるステップとを含む。
In some embodiments, the method of preparation specifically comprises
uniformly mixing a silver source and a weakly polar solvent, adding an anion source, and performing a solvent thermal reaction to obtain a silver-based quantum dot precursor (also called "silver-based quantum dot precursor");
mixing and reacting the silver-based quantum dot precursor and the metal cation source at 0-260° C. to obtain alloyed fluorescent quantum dots, the fluorescence emission peak wavelength of which is 500-1700 nm.
その中で、前記金属陽イオンとして金源が選択され、陰イオン源として硫黄源がん選択されたとき、より具体的な実施形態の１つとして、前記合金化蛍光量子ドットの調製方法は、
Ｉ、銀塩と弱極性溶媒を混合した後超音波で均一に分散させるステップと、
ＩＩ、ステップＩで最終的に得られた混合溶液に硫黄源を加えて、均一に混合および分散させた後、１００～３００℃で０．５～２４時間反応させるステップと、
ＩＩＩ、ステップＩＩの溶媒熱反応によって得られた生成物を分離し、洗浄および乾燥するステップと、
ＩＶ、ステップＩＩＩで得られた生成物と金源を０～２００℃で１０～７２時間反応させて、近赤外線銀金硫黄蛍光量子ドットを得るステップと、を含む。
Among them, when a gold source is selected as the metal cation source and a sulfur source cancer is selected as the anion source, as one of the more specific embodiments, the method for preparing the alloyed fluorescent quantum dots comprises:
I. a step of uniformly dispersing with ultrasonic waves after mixing the silver salt and the weakly polar solvent;
II, adding a sulfur source to the mixed solution finally obtained in step I, uniformly mixing and dispersing, and reacting at 100-300° C. for 0.5-24 hours;
III, separating, washing and drying the product obtained by the solvent thermal reaction of step II;
IV, reacting the product obtained in step III with the gold source at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-sulfur fluorescent quantum dots;
本出願で調製された最終生成物である合金化蛍光量子ドットは、サイズ分布が均一であり、その蛍光発光ピーク波長が５００～１７００ｎｍ、好ましくは８００～１３５０ｎｍにあり、非常に高い絶対蛍光量子効率（８５％を超える）を有すると同時に、有毒な重金属元素を含まない。そして、最終生成物の収率が高く、調製プロセスは反応規模を容易に拡大することができる。 The final product alloyed fluorescent quantum dots prepared in this application have a uniform size distribution, their fluorescence emission peak wavelengths are between 500 and 1700 nm, preferably between 800 and 1350 nm, and very high absolute fluorescence quantum efficiencies. (greater than 85%) and does not contain toxic heavy metal elements. And the yield of the final product is high, and the preparation process can be easily scaled up.
本出願の技術的解決策の別の側面として、前記方法によって調製された合金化蛍光量子ドットに関し、その形態サイズが均一で、絶対量子収率が高く、有毒な重金属元素を含まないため、生物学的画像化、生物医学または近赤外線デバイス分野などにおいて重要な応用見通しを持っている。 Another aspect of the technical solution of the present application relates to the alloyed fluorescent quantum dots prepared by the above method, which have uniform morphology size, high absolute quantum yield, and do not contain toxic heavy metal elements, which are It has important application prospects in scientific imaging, biomedical or near-infrared device fields.
さらに、前記合金化蛍光量子ドットは、好ましくはＡｇＡｕＳｅ、ＡｇＡｕＳ、ＡｇＡｕＴｅ、ＣｕＡｇＳ、ＣｕＡｇＳｅ、ＡｇＩｎＴｅ２などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, the alloyed fluorescent quantum dots preferably include, but are not limited to, any one or a combination of two or more of AgAuSe, AgAuS, AgAuTe, CuAgS, CuAgSe, AgInTe2 .
さらに、前記合金化蛍光量子ドットは、ドープされた合金化蛍光量子ドットを含み、例えば、好ましくはマンガンドープされたセレン化銀蛍光量子ドット、ニッケルドープされたテルル化銀蛍光量子ドット、インジウムドープされた硫化銀蛍光量子ドット、コバルトドープされた硫化銀蛍光量子ドットなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Further, said alloyed fluorescent quantum dots include doped alloyed fluorescent quantum dots, such as preferably manganese-doped silver selenide fluorescent quantum dots, nickel-doped silver telluride fluorescent quantum dots, indium-doped including, but not limited to, any one or a combination of two or more of silver sulfide fluorescent quantum dots, cobalt-doped silver sulfide fluorescent quantum dots, and the like.
さらに、前記合金化蛍光量子ドットはコアシェル構造を有し、例えば、前記合金化蛍光量子ドットは好ましくはＡｇ２Ｓ＠ＺｎＳ、Ａｇ２Ｔｅ＠Ａｇ２Ｓ、Ａｇ２Ｔｅ＠Ａｇ２Ｓｅ、Ａｇ２Ｓｅ＠Ａｇ２Ｓ、Ａｇ２Ｓｅ＠Ａｇ２Ｔｅ、Ａｇ２Ｓ＠Ａｇ２Ｓｅ、Ａｇ２Ｓ＠Ａｇ２Ｔｅ、Ａｇ２Ｓｅ＠ＺｎＳ、Ａｇ２Ｓｅ＠ＺｎＳｅ、Ａｇ２Ｓ＠ＭｎＳなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 Furthermore, the alloyed fluorescent quantum dots have a core-shell structure, for example, the alloyed fluorescent quantum dots are preferably Ag2S @ZnS, Ag2Te @ Ag2S , Ag2Te @ Ag2Se , Ag2 Se@ Ag2S , Ag2Se @ Ag2Te , Ag2S@Ag2Se , Ag2S@ Ag2Te , Ag2Se @ ZnS , Ag2Se @ ZnSe, Ag2S @MnS, etc. or any combination of two or more.
本出願の実施例の別の側面は、近赤外線銀金セレン蛍光量子ドットの調製方法をさらに提供し、この方法は、
銀源、セレン源、弱極性溶媒を含む第３の均一混合反応体系を溶媒熱反応させ、セレン化銀量子ドット前駆体を調製するステップと、
セレン化銀量子ドット前駆体、金源を含む第４の均一混合反応体系を０～２００℃で１０～７２時間陽イオン交換反応させて、近赤外線銀金セレン蛍光量子ドットを取得するステップと、を含む。
Another aspect of the embodiments of the present application further provides a method of preparing near-infrared silver gold selenium fluorescent quantum dots, the method comprising:
Solvothermally reacting a third homogeneous mixed reaction system comprising a silver source, a selenium source, and a weakly polar solvent to prepare a silver selenide quantum dot precursor;
a fourth homogeneous mixed reaction system comprising a silver selenide quantum dot precursor and a gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots; including.
いくつかの実施形態では、前記調製方法は、主に、銀源とセレン源を弱極性溶媒に均一に混合して溶媒熱反応させ、セレン化銀量子ドットを得、上記のセレン化銀量子ドットと金源を混合し、室温で陽イオン交換反応させて、高量子効率の近赤外線銀金セレン量子ドットを得、その蛍光発光ピーク波長が８００～１７００ｎｍであることを含む。 In some embodiments, the preparation method mainly consists of uniformly mixing a silver source and a selenium source in a weakly polar solvent for solvent thermal reaction to obtain silver selenide quantum dots, and the above silver selenide quantum dots and a gold source, followed by a cation exchange reaction at room temperature to obtain near-infrared silver-gold-selenium quantum dots with high quantum efficiency, whose fluorescence emission peak wavelength is 800-1700 nm.
いくつかの好ましい実施形態では、前記高量子効率の近赤外線銀金セレン蛍光量子ドットの調製方法は、具体的に、
銀源と弱極性溶媒を均一に混合しセレン源を加えて溶媒熱反応させ、セレン化銀量子ドット前駆体を調製するステップと、
前記セレン化銀前駆体と金源を０～２００℃で混合し反応させ、銀金セレン蛍光量子ドットを得、その蛍光発光ピーク波長が８００～１７００ｎｍで、絶対蛍光量子収率が９０％を超えるステップを含む。
In some preferred embodiments, the method for preparing high quantum efficiency near-infrared silver gold selenium fluorescent quantum dots specifically comprises:
uniformly mixing a silver source and a weakly polar solvent, adding a selenium source and causing a solvent thermal reaction to prepare a silver selenide quantum dot precursor;
The silver selenide precursor and the gold source are mixed and reacted at 0-200° C. to obtain silver-gold-selenium fluorescent quantum dots, which have a fluorescence emission peak wavelength of 800-1700 nm and an absolute fluorescence quantum yield of more than 90%. Including steps.
いくつかの実施形態では、前記調製方法は、まず銀源と弱極性溶媒を均一に混合し、次にセレン源を加え、前記第３の均一混合反応体系を形成するステップをさらに含む。 In some embodiments, the preparation method further comprises first homogeneously mixing a silver source and a weakly polar solvent, and then adding a selenium source to form the third homogeneous mixed reaction system.
いくつかの実施形態では、前記調製方法は具体的に、前記第３の均一混合反応体系を１００～３００℃で０．５～２４時間溶媒熱反応させ、前記セレン化銀量子ドット前駆体を得るステップを含む。 In some embodiments, the preparation method specifically comprises solvothermally reacting the third homogeneous mixed reaction system at 100-300° C. for 0.5-24 hours to obtain the silver selenide quantum dot precursor. Including steps.
いくつかの実施形態では、前記銀源とセレン源の質量比は１～１０：１～１０である。つまり、前記調製方法は、質量比１～１０：１～１０の銀源とセレン源溶を弱極性溶媒に溶解するステップを含む。 In some embodiments, the weight ratio of the silver source to the selenium source is 1-10:1-10. That is, the preparation method includes dissolving a silver source and a selenium source in a weight ratio of 1-10:1-10 in a weakly polar solvent.
本出願によって提供されるセレン化銀前駆体の調製プロセスは溶媒熱反応であり、ステップが簡単で、実験条件を制御しやすく、使用される試薬を簡単に入手でき、最終生成物の収率が高く、大規模生産に適している。 The silver selenide precursor preparation process provided by this application is a solvent thermal reaction with simple steps, easy control of experimental conditions, easy availability of the reagents used, and high yields of the final product. High and suitable for large-scale production.
いくつかの実施形態では、前記調製方法は、セレン化銀量子ドット前駆体、金源と弱極性溶媒を均一に混合し、前記第４の均一混合反応体系を形成するステップを含む。 In some embodiments, the preparation method includes uniformly mixing a silver selenide quantum dot precursor, a gold source, and a weakly polar solvent to form the fourth homogeneous mixed reaction system.
いくつかの実施形態では、前記セレン化銀量子ドット前駆体と金源の質量比は１～１０：１～１０である。つまり、前記調製方法は、質量比１～１０：１～１０のセレン化銀量子ドット前駆体と金源を弱極性溶媒に溶解するステップを含む。 In some embodiments, the weight ratio of said silver selenide quantum dot precursor to gold source is 1-10:1-10. That is, the preparation method includes dissolving a silver selenide quantum dot precursor and a gold source in a weight ratio of 1-10:1-10 in a weakly polar solvent.
いくつかの実施形態では、前記銀塩は塩化銀、臭化銀、ヨウ化銀、硫酸銀、硝酸銀、炭酸銀、硫化銀、トリフルオロ酢酸銀、ジエチルジチオカルバミン酸銀などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, the silver salt is any one or two of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate, silver diethyldithiocarbamate, and the like. Including but not limited to combinations of one or more.
いくつかの実施形態では、前記セレン源は二酸化セレン、セレン粉末、セレン酸ナトリウム、亜セレン酸ナトリウム、セレン化ナトリウム、ジフェニルジセレニドなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, the selenium source comprises any one or a combination of two or more of selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide, diphenyldiselenide, etc. It is not limited to these.
いくつかの実施形態では、前記弱極性溶媒はオレイルアミン、オレイン酸、オクタデセン、オクタデシルアミン、ドデシルアミン、テトラデシルアミン、ドデカンチオール、オクタンチオ、オクタデカンチオールなどのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, the weakly polar solvent comprises any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethio, octadecanethiol, and the like. but not limited to these.
いくつかの実施形態では、前記金源はクロロ金酸ナトリウム、クロロ金酸、硝酸金、塩化金、水酸化金、酸化金、金ナノロッド、金粒子などのいずれか１つまたは２つ以上の組み合わせを含むが、これらに限定されない。 In some embodiments, the gold source is any one or a combination of two or more of sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods, gold particles, and the like. including but not limited to.
前記銀塩、セレン源、弱極性溶媒と金源などは上記のものから選択できるが、それらに限定されない。 The silver salt, selenium source, weakly polar solvent and gold source can be selected from the above, but are not limited thereto.
さらに、典型的な実施例では、前記調製方法は、まず硝酸銀をオレイルアミンに溶解し、セレン源を加え、１００～３００℃で１～６時間反応させた後、洗浄して、標的生成物であるセレン化銀量子ドット前駆体を得るステップを含む。 Further, in a typical embodiment, the preparation method firstly dissolves silver nitrate in oleylamine, adds selenium source, reacts at 100-300° C. for 1-6 hours, and then rinses to obtain the target product. Obtaining a silver selenide quantum dot precursor.
さらに、前記銀塩とセレン源の質量比は０．１～１ｇ：０．１～１ｇである。 Further, the mass ratio of the silver salt and the selenium source is 0.1-1 g:0.1-1 g.
いくつかのより好ましい実施形態では、前記調製方法は、質量０．１～１ｇの銀塩を弱極性溶媒に溶解するステップを含み得る。 In some more preferred embodiments, the preparation method may comprise dissolving 0.1-1 g mass of silver salt in a weakly polar solvent.
さらに、前記調製方法は具体的に、前記セレン化銀前駆体と金源を混合し、１００～２００℃で反応させて、近赤外線銀金セレン蛍光量子ドットを得るステップを含む。 Further, the preparation method specifically includes the steps of mixing the silver selenide precursor and the gold source and reacting them at 100-200° C. to obtain near-infrared silver gold selenide fluorescent quantum dots.
さらに、前記調製方法は、反応が完了した後、得られた銀金セレン蛍光量子ドットを洗浄するステップをさらに含む。 Moreover, the preparation method further comprises washing the obtained silver gold selenium fluorescent quantum dots after the reaction is completed.
その中で、より具体的な実施形態の１つとして、前記調製方法は、
Ｉ、銀塩と弱極性溶媒を混合した後超音波で均一に分散させるステップと、
ＩＩ、ステップＩで最終的に得られた混合溶液にセレン源を加え均一に混合および分散させた後、１００～３００℃で０．５～２４時間反応させるステップと、
ＩＩＩ、ステップＩＩの溶媒熱反応によって得られた生成物を分離し、洗浄および乾燥するステップと、
ＩＶ、ステップＩＩＩで得られた生成物と金源を０～２００℃で１０～７２時間反応させて、前記近赤外線銀金セレン蛍光量子ドットを得るステップと、を含む。
Among them, as one of the more specific embodiments, the preparation method comprises:
I. a step of uniformly dispersing with ultrasonic waves after mixing the silver salt and the weakly polar solvent;
II, a step of adding a selenium source to the mixed solution finally obtained in step I, uniformly mixing and dispersing, and reacting at 100 to 300° C. for 0.5 to 24 hours;
III, separating, washing and drying the product obtained by the solvent thermal reaction of step II;
IV, reacting the product obtained in step III with a gold source at 0-200° C. for 10-72 hours to obtain the near-infrared silver-gold-selenium fluorescent quantum dots;
本出願は、まず簡単な高温ソルボサーマル法によってセレン化銀量子ドットを調製し、次に陽イオン交換法によって銀金セレン量子ドットを得、その合成プロセスステップは簡単で、実験条件を制御しやすく、使用される試薬を簡単に入手でき、最終生成物の収率が高く、大規模生産に適している。 This application first prepares silver-selenide quantum dots by a simple high-temperature solvothermal method, and then obtains silver-gold-selenium quantum dots by a cation exchange method, the synthesis process steps are simple, and the experimental conditions are easy to control. , the reagents used are readily available, the yield of the final product is high, and it is suitable for large-scale production.
本出願で調製された最終生成物である近赤外線銀金セレン蛍光量子ドットは、サイズ分布が均一で、その蛍光発光ピーク波長が８００～１７００ｎｍ、好ましくは８００～１３５０ｎｍにあり、非常に高い絶対蛍光量子効率（９０％を超える）を有すると同時に、有毒な重金属元素を含まない。最終生成物の収率が高く、調製プロセスは反応規模を容易に拡大することができる。 The final product, the near-infrared silver gold selenium fluorescent quantum dots prepared in this application, has a uniform size distribution, its fluorescence emission peak wavelength is between 800 and 1700 nm, preferably between 800 and 1350 nm, and has a very high absolute fluorescence. It has quantum efficiency (over 90%) and at the same time does not contain toxic heavy metal elements. The yield of the final product is high and the preparation process can be easily scaled up.
さらに、本出願の調製プロセスは、他の近赤外線銀金セレン蛍光量子ドットの調製プロセスにも適用され得、収率が高く、反応規模を容易に拡大することができる。 In addition, the preparation process of the present application can also be applied to the preparation process of other near-infrared silver gold selenium fluorescent quantum dots, with high yield and easy scale-up of reaction.
本出願の技術的解決策の別の側面は、前記方法によって調製された近赤外線銀金セレン蛍光量子ドットに関する。 Another aspect of the technical solution of the present application relates to near-infrared silver gold selenium fluorescent quantum dots prepared by said method.
さらに、前記近赤外線銀金セレン蛍光量子ドットの直径は２～２０ｎｍである。 Further, the diameter of the near-infrared silver gold selenium fluorescent quantum dots is 2-20 nm.
さらに、前記近赤外線銀金セレン蛍光量子ドットの蛍光発光ピーク波長が８００～１７００ｎｍ、好ましくは８００～１３５０ｎｍであり、絶対蛍光量子収率が９０％を超える同時に、有毒な重金属元素を含まない。 Further, the near-infrared silver gold selenium fluorescent quantum dots have a fluorescence emission peak wavelength of 800-1700 nm, preferably 800-1350 nm, an absolute fluorescence quantum yield of more than 90%, and do not contain toxic heavy metal elements.
本出願の技術的解決策の別の側面として、本出願は、近赤外線銀金セレン蛍光量子ドットをさらに提供し、その形態サイズが均一であり、絶対量子収率が高く、有毒な重金属元素を含まないため、生物学的画像化、生物医学または近赤外線デバイス分野などにおいて重要な応用見通しを持っている。 As another aspect of the technical solution of the present application, the present application further provides near-infrared silver gold selenium fluorescent quantum dots, whose morphology size is uniform, absolute quantum yield is high, and toxic heavy metal elements are Since it does not contain, it has important application prospects in biological imaging, biomedicine or near-infrared device fields.
本出願の実施例の別の側面は、前記の任合金化蛍光量子ドットまたは近赤外線銀金セレン蛍光量子ドットの生物学的画像化、生物医学または近赤外線デバイス等分野中の用途に関する。 Another aspect of the embodiments of the present application relates to the use of said alloyed fluorescent quantum dots or near infrared silver gold selenium fluorescent quantum dots in fields such as biological imaging, biomedical or near infrared devices.
さらに、前記近赤外線デバイスは可以是近赤外線発光ダイオード、太陽電池、光検出器、レーザー等、これらに限定されない。 Further, the near-infrared device can be a near-infrared light emitting diode, a solar cell, a photodetector, a laser, etc., but not limited to these.
以上のように、上記の技術的解決策により、本出願はまず簡単な高温ソルボサーマル法によって銀系量子ドットを調製し、次にイオン交換法によって合金化量子ドットを得、その合成プロセスは簡単で制御しやすく、収率が高く、大規模に調製可能であり、蛍光発光が可視光から近赤外線までにあり調整可能であり、優れた光安定性を有すると同時に、有毒な重金属元素を含まないため、生物学的画像化、近赤外線デバイスなどの分野で幅広い用途の見通しを持っている。 In summary, according to the above technical solutions, the present application first prepares silver-based quantum dots by a simple high-temperature solvothermal method, then obtains alloyed quantum dots by an ion-exchange method, and its synthesis process is simple They are easy to control with high yields, can be prepared on a large scale, have tunable fluorescence emissions from the visible to the near-infrared, have excellent photostability, and contain toxic heavy metal elements. Therefore, it has broad application prospects in areas such as biological imaging and near-infrared devices.
本出願の目的、技術的解決策および利点をより明確にするために、以下、いくつかの好ましい実施例と併せて本出願の技術的解決策をさらに具体的に説明するが、本出願は下記の実施例に限定されず、当業者は本出願の主な指導思想の下で加えた非本質的な改善および調整は、依然として本出願の保護範囲に含まれる。特に明記しない限り、下記の実施例で使用される様々な試薬は当業者に周知であり、市場購入などを通じて入手することができる。下記の実施例で提示しない具体的な条件の実験方法は通常、従来の通常条件または製造業者の推奨条件下で行われる。 In order to make the purpose, technical solution and advantages of the present application clearer, the technical solution of the present application will be described in more detail below together with some preferred embodiments, while the present application is as follows: , and non-essential improvements and adjustments made by those skilled in the art under the main guiding idea of the present application still fall within the protection scope of the present application. Unless otherwise stated, the various reagents used in the examples below are well known to those of skill in the art and are available through commercial purchases and the like. Experimental procedures with specific conditions not presented in the examples below are generally performed under conventional normal conditions or manufacturer's recommended conditions.
（実施例１）
０．０６ｇの硝酸銀を２０ｍＬのオレイルアミンに溶解し、超音波で均一に分散し、次に０．０６の硫黄粉末を加え、２００℃で５時間反応させ、硫化銀前駆体を得、そして０．０６ｇのクロロ金酸を加え、１００℃で４８時間反応させ、銀金硫黄蛍光量子ドットを得る。
(Example 1)
Dissolve 0.06 g of silver nitrate in 20 mL of oleylamine, disperse evenly with ultrasonic waves, then add 0.06 g of sulfur powder, react at 200° C. for 5 hours to obtain a silver sulfide precursor, and 0.06 g of silver nitrate. Add 06 g of chloroauric acid and react at 100° C. for 48 hours to obtain silver gold sulfur fluorescent quantum dots.
図１から分かるように、本実施例で得られた近赤外線銀金硫黄蛍光量子ドット生成物の形態サイズは均一であり、サイズが約４．５ｎｍである。 As can be seen from FIG. 1, the morphology size of the near-infrared silver-gold-sulfur fluorescent quantum dot product obtained in this example is uniform, with a size of about 4.5 nm.
上記銀金硫黄量子ドットをクロロホルムに分散させる。図２に示すように、可視-近赤外線吸収分光計を使用してその吸収スペクトルを測定したとこり、量子ドットが可視から近赤外線の領域まで強い吸収を示す。さらに近赤外線蛍光分光計を使用してその発光スペクトルおよび絶対蛍光量子収率を測定する。図３から分かるように、この銀金硫黄蛍光量子ドットの発光が８００～１１００ｎｍにあり、図４から分かるようにその絶対量子効率が８５．１５％である。 The silver gold sulfur quantum dots are dispersed in chloroform. As shown in Figure 2, the absorption spectrum was measured using a visible-near infrared absorption spectrometer, and the quantum dots show strong absorption from the visible to the near infrared region. Furthermore, a near-infrared fluorescence spectrometer is used to measure its emission spectrum and absolute fluorescence quantum yield. As can be seen from FIG. 3, the emission of this silver-gold-sulfur fluorescent quantum dot is in the range of 800-1100 nm, and its absolute quantum efficiency is 85.15%, as can be seen from FIG.
（実施例２）
０．０６ｇの酢酸銀を２０ｍＬオレイン酸に溶解し、超音波で均一に分散し、次に０．６の硫黄粉末を加え、２５０℃で０．５時間反応させ、硫化銀前駆体を得、そして０．６ｇ塩化第一銅を加え、２００℃で１０時間反応させ、銀銅硫蛍光量子ドットを得る。
(Example 2)
Dissolve 0.06 g of silver acetate in 20 mL of oleic acid, disperse uniformly with ultrasonic waves, then add 0.6 of sulfur powder and react at 250° C. for 0.5 hours to obtain a silver sulfide precursor, Then, 0.6 g of cuprous chloride is added and reacted at 200° C. for 10 hours to obtain silver-copper-sulfur fluorescent quantum dots.
（実施例３）
０．６ｇの硝酸銀を２０ｍＬのオクタデカンチオールに溶解し、超音波で均一に分散し、次に０．６ｇ テルル粉末を加え、１５０℃で５時間反応させ、テルル化銀前駆体を得、そして０．６ｇセレン粉末を加え、１００℃で２４時間反応させ、銀セレンテルル蛍光量子ドットを得る。
(Example 3)
Dissolve 0.6 g of silver nitrate in 20 mL of octadecanethiol, disperse evenly with ultrasonic waves, then add 0.6 g of tellurium powder, react at 150° C. for 5 hours to obtain a silver telluride precursor, and Add .6 g selenium powder and react at 100° C. for 24 hours to obtain silver selenite tellurium fluorescent quantum dots.
（実施例４）
０．０６ｇのトリフルオロ酢酸銀を２０ｍＬのドデシルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、１８０℃で１０時間反応させ、セレン化銀前駆体を得、そして０．０６ｇのクロロ白金酸を加え、０℃で７２時間反応させ、銀白金セレン蛍光量子ドットを得る。
(Example 4)
0.06 g of silver trifluoroacetate is dissolved in 20 mL of dodecylamine and dispersed uniformly by ultrasonic waves, then 0.06 g of selenium powder is added and reacted at 180° C. for 10 hours to convert the silver selenide precursor. Then add 0.06 g of chloroplatinic acid and react at 0° C. for 72 hours to obtain silver platinum selenium fluorescent quantum dots.
（実施例５）
０．０６ｇの塩化銀を２０ｍＬのオクタンチオに溶解し、超音波で均一に分散し、次に０．６ｇの硫黄粉末を加え、２００℃で１２時間反応させ、硫化銀前駆体を得、そして０．０６ｇの塩化第一鉄を加え、０℃で７２時間反応させ、銀鉄セレン蛍光量子ドットを得る。
(Example 5)
Dissolve 0.06 g of silver chloride in 20 mL of octanethio, disperse uniformly with ultrasonic waves, then add 0.6 g of sulfur powder, react at 200° C. for 12 hours to obtain a silver sulfide precursor, and Add 0.06 g of ferrous chloride and react at 0° C. for 72 hours to obtain silver iron selenium fluorescent quantum dots.
（実施例６）
０．６ｇの硫化銀を２０ｍＬのヘキサデシルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、２００℃で５時間反応させ、セレン化銀前駆体を得、そして０．０６ｇの塩化パラジウムを加え、０℃で７２時間反応させ、パラジウム銀セレン蛍光量子ドットを得る。
(Example 6)
0.6 g of silver sulfide was dissolved in 20 mL of hexadecylamine and dispersed uniformly with ultrasonic waves, then 0.06 g of selenium powder was added and reacted at 200° C. for 5 hours to obtain a silver selenide precursor. , and then add 0.06 g of palladium chloride and react at 0° C. for 72 hours to obtain palladium-silver-selenium fluorescent quantum dots.
（実施例７）
０．０６ｇのヨウ化銀を２０ｍＬのオレイルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、２００℃で５時間反応させ、セレン化銀前駆体を得、そして０．０６ｇの塩化マンガンを加え、０℃で７２時間反応させ、マンガンドープされたセレン化銀蛍光量子ドットを得る。
(Example 7)
0.06 g of silver iodide was dissolved in 20 mL of oleylamine and dispersed uniformly with ultrasonic waves, then 0.06 g of selenium powder was added and reacted at 200° C. for 5 hours to obtain a silver selenide precursor, Then, 0.06 g of manganese chloride is added and reacted at 0° C. for 72 hours to obtain manganese-doped silver selenide fluorescent quantum dots.
（実施例８）
０．０６ｇの酢酸銀を２０ｍＬのオレイルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、３００℃で０．５時間反応させ、セレン化銀前駆体を得、そして０．０６ｇの硫黄粉末を加え、１００℃で７２時間反応させ、Ａｇ２Ｓｅ＠Ａｇ２Ｓ蛍光量子ドットを得る。
(Example 8)
0.06 g of silver acetate was dissolved in 20 mL of oleylamine and dispersed uniformly with ultrasonic waves, then 0.06 g of selenium powder was added and reacted at 300° C. for 0.5 hours to obtain a silver selenide precursor. , and add 0.06 g of sulfur powder and react at 100° C. for 72 hours to obtain Ag 2 Se@Ag 2 S fluorescent quantum dots.
（実施例９）
０．６ｇの硫酸銀を２０ｍＬのオクタデカンチオールに溶解し、超音波で均一に分散し、次に０．０６ｇのテルル粉末を加え、１５０℃で１時間反応させ、テルル化銀前駆体を得、そして０．６ｇの硫黄粉末と０．０６ｇの酢酸亜鉛を加え、２６０℃で０．４時間反応させ、Ａｇ２Ｔｅ＠ＺｎＳ蛍光量子ドットを得る。
(Example 9)
0.6 g of silver sulfate is dissolved in 20 mL of octadecanethiol and dispersed uniformly with ultrasonic waves, then 0.06 g of tellurium powder is added and reacted at 150° C. for 1 hour to obtain a silver telluride precursor, Then 0.6 g of sulfur powder and 0.06 g of zinc acetate are added and reacted at 260° C. for 0.4 hours to obtain Ag 2 Te@ZnS fluorescent quantum dots.
（実施例１０）
０．５ｇのジエチルジチオカルバミン酸銀を２０ｍＬのオクタデカンチオールに溶解し、超音波で均一に分散し、次に０．０６ｇのテルル粉末を加え、２００℃で１時間反応させ、テルル化銀前駆体を得、そして０．０６ｇの酢酸ニッケルを加え、１５０℃で２時間反応させ、ニッケルドープされたテルル化銀蛍光量子ドットを得る。
(Example 10)
0.5 g of silver diethyldithiocarbamate is dissolved in 20 mL of octadecanethiol and dispersed uniformly by ultrasonic waves, then 0.06 g of tellurium powder is added and reacted at 200° C. for 1 hour to form a silver telluride precursor. and add 0.06 g of nickel acetate and react at 150° C. for 2 hours to obtain nickel-doped silver telluride fluorescent quantum dots.
（実施例１１）
０．０４ｇの酢酸銀を２０ｍＬのドデカンチオールに溶解し、超音波で均一に分散し、次に０．０６ｇの硫黄粉末を加え、２００℃で１時間反応させ、硫化銀前駆体を得、そして０．０６ｇの酢酸インジウムを加え、１５０℃で２時間反応させ、インジウムドープされた硫化銀蛍光量子ドットを得る。
(Example 11)
Dissolve 0.04 g of silver acetate in 20 mL of dodecanethiol, disperse evenly with ultrasonic waves, then add 0.06 g of sulfur powder, react at 200° C. for 1 hour to obtain a silver sulfide precursor, and Add 0.06 g of indium acetate and react at 150° C. for 2 hours to obtain indium-doped silver sulfide fluorescent quantum dots.
（実施例１２）
０．０６ｇの炭酸銀を２０ｍＬのドデカンチオールに溶解し、超音波で均一に分散し、次に０．０６の硫黄粉末を加え、１００℃で２４時間反応させ、硫化銀前駆体を得、そして０．０６ｇの塩化コバルトを加え、１００℃で４８時間反応させ、コバルトドープされた硫化銀蛍光量子ドットを得る。
(Example 12)
Dissolve 0.06 g of silver carbonate in 20 mL of dodecanethiol, disperse evenly with ultrasonic waves, then add 0.06 g of sulfur powder, react at 100° C. for 24 hours to obtain a silver sulfide precursor, and Add 0.06 g of cobalt chloride and react at 100° C. for 48 hours to obtain cobalt-doped silver sulfide fluorescent quantum dots.
さらに、本願の発明者は前記の他の原料およびその他のプロセス条件などを用いて実施例１～１２中の様々な原料および対応のプロセス条件を置換して対応の実験を行い、得られた合金化蛍光量子ドットの形態、性能なども理想的であり、実施例１～１２の製品と基本的に同じである。 Furthermore, the inventors of the present application conducted corresponding experiments by substituting various raw materials and corresponding process conditions in Examples 1 to 12 using other raw materials and other process conditions, etc., and obtained alloys The morphology and performance of the fluorescent quantum dots are also ideal, and are basically the same as the products of Examples 1-12.
（実施例１３）
０．０６ｇの硝酸銀を２０ｍＬのオレイルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、２００℃で５時間反応させ、セレン化銀量子ドット前駆体（０．６ｇ）を得、そして０．０６ｇのクロロ金酸を加え、１００℃で４８時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 13)
0.06 g of silver nitrate was dissolved in 20 mL of oleylamine and dispersed uniformly with ultrasonic waves, then 0.06 g of selenium powder was added and reacted at 200° C. for 5 hours to obtain a silver selenide quantum dot precursor (0.06 g). 6g), and add 0.06g of chloroauric acid and react at 100°C for 48 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
図５ａ～図５ｂから分かるように、本実施例で得られた近赤外線銀金セレン蛍光量子ドットの生成物の形態サイズは均一であり、サイズが約４．８ｎｍであり、図５ａは近赤外線銀金セレン蛍光量子ドットの透過電子顕微鏡写真であり、図５ｂは高分解能透過電子顕微鏡写真である。図６および図７を参照すると、粉末Ｘ線回折およびエネルギー分散Ｘ線スペクトル図から分かるように、このナノ粒子材料は銀金セレン化合物である。 It can be seen from FIGS. 5a-5b that the morphology and size of the product of near-infrared silver gold selenium fluorescent quantum dots obtained in this example are uniform, with a size of about 4.8 nm, and FIG. FIG. 5b is a transmission electron micrograph of silver gold selenium fluorescent quantum dots and FIG. 5b is a high resolution transmission electron micrograph. 6 and 7, the nanoparticle material is a silver-gold-selenium compound, as can be seen from the powder X-ray diffraction and energy-dispersive X-ray spectrum diagrams.
上記銀金セレン量子ドットをクロロホルムに分散させる。近赤外線蛍光分光計を使用してその発光スペクトルと絶対蛍光量子収率を測定する。図８ａ～図８ｂから分かるように、この銀金セレン蛍光量子ドットの発光が８００～１２００ｎｍにあり、絶対量子効率が９０．３％である。 The silver gold selenium quantum dots are dispersed in chloroform. Measure its emission spectrum and absolute fluorescence quantum yield using a near-infrared fluorescence spectrometer. As can be seen from FIGS. 8a-8b, the emission of the silver-gold-selenium fluorescent quantum dots lies between 800 and 1200 nm, with an absolute quantum efficiency of 90.3%.
（実施例１４）
０．０６ｇの炭酸銀を２０ｍＬのオクタンチオに溶解し、超音波で均一に分散し、次に０．８ｇの二酸化セレンを加え、２５０℃で２時間反応させ、セレン化銀量子ドット前駆体（０．０５ｇ）を得、そして０．５ｇの硝酸金を加え、２００℃で１０時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 14)
0.06 g of silver carbonate is dissolved in 20 mL of octanethio, and dispersed uniformly with ultrasonic waves, then 0.8 g of selenium dioxide is added and reacted at 250° C. for 2 hours to form a silver selenide quantum dot precursor (0 0.05 g), and add 0.5 g of gold nitrate and react at 200° C. for 10 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
（実施例１５）
０．６ｇの臭化銀を２０ｍＬのオレイン酸に溶解し、超音波で均一に分散し、次に０．６ｇのセレン酸ナトリウムを加え、２００℃で１時間反応させ、セレン化銀量子ドット前駆体（０．１ｇ）を得、そして０．１ｇのクロロ金酸ナトリウムを加え、１００℃で４８時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 15)
0.6 g of silver bromide was dissolved in 20 mL of oleic acid and dispersed uniformly with ultrasonic waves, then 0.6 g of sodium selenate was added and reacted at 200° C. for 1 hour to form a silver selenide quantum dot precursor. (0.1 g), then add 0.1 g of sodium chloroaurate and react at 100° C. for 48 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
（実施例１６）
０．０６ｇの塩化銀を２０ｍＬのドデカンチオールに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン化ナトリウムを加え、１００℃で５時間反応させ、セレン化銀量子ドット前駆体（０．０６ｇ）を得、そして０．０６ｇの塩化金を加え、０℃で７２時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 16)
Dissolve 0.06 g of silver chloride in 20 mL of dodecanethiol, and disperse evenly with ultrasonic waves, then add 0.06 g of sodium selenide and react at 100° C. for 5 hours to obtain a silver selenide quantum dot precursor. (0.06 g), and add 0.06 g of gold chloride and react at 0° C. for 72 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
（実施例１７）
０．０６ｇのヨウ化銀を２０ｇオクタデシルアミンに溶解し、超音波で均一に分散し、次に０．０６ｇのジフェニルジセレニドを加え、２００℃で２４時間反応させ、セレン化銀量子ドット前駆体（０．０３ｇ）を得、そして０．０５ｇの水酸化金を加え、０℃で７２時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 17)
0.06 g of silver iodide is dissolved in 20 g of octadecylamine, dispersed uniformly by ultrasonic waves, then 0.06 g of diphenyldiselenide is added and reacted at 200° C. for 24 hours to form a silver selenide quantum dot precursor. (0.03 g), then add 0.05 g of gold hydroxide and react at 0° C. for 72 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
（実施例１８）
０．０６ｇのジエチルジチオカルバミン酸銀を２０ｍＬのオクタデカンチオールに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、３００℃で０．５時間反応させ、セレン化銀量子ドット前駆体（０．０６ｇ）を得、そして０．０６ｇの酸化金を加え、０℃で７２時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 18)
Dissolve 0.06 g of silver diethyldithiocarbamate in 20 mL of octadecanethiol, disperse evenly with ultrasonic waves, then add 0.06 g of selenium powder, react at 300° C. for 0.5 hours, and add silver selenide quantum A dot precursor (0.06 g) is obtained, and 0.06 g of gold oxide is added and reacted at 0° C. for 72 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
（実施例１９）
０．０６ｇのトリフルオロ酢酸銀を２０ｍＬのオクタデセンに溶解し、超音波で均一に分散し、次に０．０６ｇのセレン粉末を加え、２００℃で２４時間反応させ、セレン化銀量子ドット前駆体（０．０６ｇ）を得、そして０．０６ｇの金ナノロッドを加え、０℃で７２時間反応させ、近赤外線銀金セレン蛍光量子ドットを得る。
(Example 19)
Dissolve 0.06 g of silver trifluoroacetate in 20 mL of octadecene, and evenly disperse with ultrasonic waves, then add 0.06 g of selenium powder and react at 200° C. for 24 hours to obtain a silver selenide quantum dot precursor. (0.06 g), and add 0.06 g of gold nanorods and react at 0° C. for 72 hours to obtain near-infrared silver gold selenium fluorescent quantum dots.
さらに、本願の発明者は上記の他の原料およびその他のプロセス条件などを用いて実施例１３～１９中の様々な原料および対応のプロセス条件を置換して対応の実験を行い、得られた近赤外線銀金セレン蛍光量子ドットの形態、性能なども理想的であり、実施例１３～１９の製品と基本的に同じである。 Furthermore, the inventors of the present application performed corresponding experiments by substituting various raw materials and corresponding process conditions in Examples 13-19 using other raw materials and other process conditions, etc., as described above, and obtained near-field results. The shape, performance, etc. of infrared silver gold selenium fluorescent quantum dots are also ideal, basically the same as the products of Examples 13-19.
以上のように、本出願はまず簡単な高温ソルボサーマル法によって銀系量子ドットを調製し、次にイオン交換法によって合金化量子ドットを得、その合成プロセスは簡単で制御しやすく、収率が高く、大規模に調製可能であり、蛍光発光が可視光から近赤外線までにあり調整可能であり、優れた光安定性を有すると同時に、有毒な重金属元素を含まないため、生物学的画像化、近赤外線デバイスなどの分野で幅広い用途の見通しを持っている。 In summary, the present application first prepares silver-based quantum dots by a simple high-temperature solvothermal method, and then obtains alloyed quantum dots by an ion-exchange method, the synthesis process is simple and easy to control, and the yield is High, scalable, tunable fluorescence emission from visible to near-infrared, excellent photostability, and free of toxic heavy metal elements for biological imaging , has a wide application prospect in the field of near-infrared devices and so on.
以上の実施例を使用して本出願の技術的解決策を詳細に説明したが、上記は本出願の具体的な実施例に過ぎず、本出願を制限するものではなく、本出願の原則範囲内に加えられた修正、補充や同等置換などは、すべて本出願の保護範囲に含まれるべきである。 Although the above examples are used to describe the technical solutions of the present application in detail, the above are only specific examples of the present application and are not intended to limit the application, but rather the principle scope of the application. Any modifications, additions, equivalent replacements, etc. made within the above shall all fall within the protection scope of the present application.
例示的な実施例を参照して本出願を説明したが、当業者は本出願の精神および範囲から逸脱しない限り、他の変更、省略および／または追加を加え、実質的等価物を前記実施例の要素を置換することができることは明らかである。なお、本出願の範囲から逸脱することなく、特定の場合または材料を本出願の教示に適合させるために、様々な修正を加えることができる。したがって、本明細書では、本出願を、出願を実施するために開示された特定の実施形態に限定することを意図するものではなく、本出願は、添付の特許請求の範囲に含まれるすべての実施形態を含むことを意図している。さらに、特に明記しない限り、第１、第２などの用語の使用は、順序や重要性を示すものではなく、第１、第２などの用語を使用して、ある要素を別の要素と区別するためである。 Although the present application has been described with reference to illustrative examples, those skilled in the art will appreciate that other modifications, omissions and/or additions may be made and substantially equivalents of the foregoing examples without departing from the spirit and scope of this application. It is clear that the elements of can be replaced. It should be noted that various modifications may be made to adapt a particular situation or material to the teachings of this application without departing from its scope. Accordingly, it is not intended herein to limit the application to the particular embodiments disclosed for carrying out the application, but rather to limit the application to all that falls within the scope of the appended claims. It is intended to include embodiments. Further, unless stated otherwise, the use of the terms first, second, etc. does not imply any order or significance, and the terms first, second, etc. are used to distinguish one element from another. It is for
（付記）
（付記１）
銀源、陰イオン源、弱極性溶媒を含む第１の均一混合反応体系を溶媒熱反応させ、銀系量子ドット前駆体を調製するステップと、
銀系量子ドット前駆体、陰イオン源および／または金属陽イオン源を含む第２の均一混合反応体系を０～２６０℃で０．４～７２時間イオン交換反応させて、合金化蛍光量子ドットを取得するステップと、を含むことを特徴とする合金化蛍光量子ドットの調製方法。
(Appendix)
(Appendix 1)
solvothermally reacting a first homogeneous mixed reaction system comprising a silver source, an anion source, and a weakly polar solvent to prepare a silver-based quantum dot precursor;
A second homogeneous mixed reaction system comprising a silver-based quantum dot precursor, an anion source and/or a metal cation source is subjected to an ion exchange reaction at 0-260° C. for 0.4-72 hours to form alloyed fluorescent quantum dots. A method for preparing alloyed fluorescent quantum dots, comprising: obtaining.
（付記２）
前記銀源は銀塩を含み、前記銀塩は、塩化銀、臭化銀、ヨウ化銀、硫酸銀、硝酸銀、炭酸銀、酢酸銀、硫化銀、トリフルオロ酢酸銀、ジエチルジチオカルバミン酸銀のいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする付記１に記載の調製方法。
(Appendix 2)
The silver source contains a silver salt, and the silver salt is any one of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver acetate, silver sulfide, silver trifluoroacetate, and silver diethyldithiocarbamate. or one or a combination of two or more.
（付記３）
前記陰イオン源は硫黄源、セレン源およびテルル源のいずれか１つまたは２つ以上の組み合わせを含み、好ましくは、前記硫黄源は硫黄、チオ硫酸ナトリウム、硫化ナトリウム、チオ尿素のいずれか１つまたは２つ以上の組み合わせを含み、好ましくは、前記セレン源は二酸化セレン、セレン、セレン酸ナトリウム、亜セレン酸ナトリウム、セレン化ナトリウム、ジフェニルジセレニドのいずれか１つまたは２つ以上の組み合わせを含み、好ましくは、前記テルル源はテルル、テルル酸ナトリウム、水素化テルルナトリウムのいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする付記１に記載の調製方法。
(Appendix 3)
The anion source comprises any one or a combination of two or more of a sulfur source, a selenium source and a tellurium source, preferably the sulfur source is any one of sulfur, sodium thiosulfate, sodium sulfide and thiourea. or a combination of two or more, preferably the selenium source is any one or a combination of two or more of selenium dioxide, selenium, sodium selenate, sodium selenite, sodium selenide, diphenyldiselenide Preferably, the tellurium source comprises any one or a combination of two or more of tellurium, sodium tellurate, sodium tellurium hydride.
（付記４）
前記弱極性溶媒は、オレイルアミン、オレイン酸、オクタデセン、オクタデシルアミン、ドデシルアミン、テトラデシルアミン、ドデカンチオール、オクタンチオ、オクタデカンチオールのいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする付記１に記載の調製方法。
(Appendix 4)
The weakly polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethio, and octadecanethiol. 1. The preparation method according to 1.
（付記５）
前記銀源と陰イオン源の質量比は１～１０：１～１０である、ことを特徴とする付記１に記載の調製方法。
(Appendix 5)
The preparation method according to Appendix 1, characterized in that the mass ratio of the silver source and the anion source is 1-10:1-10.
（付記６）
前記溶媒熱反応の温度は１００～３００℃であり、時間は０．５～２４時間である、ことを特徴とする付記１に記載の調製方法。
(Appendix 6)
The preparation method according to Appendix 1, characterized in that the temperature of the solvent heat reaction is 100-300° C. and the time is 0.5-24 hours.
（付記７）
前記銀系量子ドット前駆体は、Ａｇ２Ｓ、Ａｇ２Ｓｅ、Ａｇ２Ｔｅのいずれか１つまたは２つ以上の組み合わせを含み、および／または、前記銀系量子ドット前駆体と金属陽イオン源の質量比は１～１０：１～１０である、ことを特徴とする付記１に記載の調製方法。
(Appendix 7)
The silver-based quantum dot precursor includes any one or a combination of two or more of Ag 2 S, Ag 2 Se, Ag 2 Te, and/or the silver-based quantum dot precursor and a metal cation source The preparation method according to Appendix 1, wherein the mass ratio of is 1-10:1-10.
（付記８）
前記金属陽イオン源に含まれる金属元素は、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｕ、Ｐｄ、Ｐｔ、Ｉｎのいずれか１つまたは２つ以上の組み合わせを含み、好ましくは、前記金属陽イオン源は塩化第二鉄、塩化第一鉄、硫酸第二鉄、硫酸第一鉄、硝酸鉄、塩化コバルト、硝酸コバルト、硫酸コバルト、酢酸コバルト、塩化ニッケル、硝酸ニッケル、硫酸ニッケル、酢酸ニッケル、硫酸銅、酢酸銅、硝酸銅、塩化第二銅、塩化第一銅、酢酸亜鉛、硝酸亜鉛、硫酸亜鉛、塩化亜鉛、クロロ金酸ナトリウム、クロロ金酸、硝酸金、塩化金、水酸化金、酸化金、酢酸パラジウム、硝酸パラジウム、塩化パラジウム、クロロ白金酸、クロロ白金酸ナトリウム、クロロ白金酸カリウム、酢酸インジウム、塩化インジウムのいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする付記１に記載の調製方法。
(Appendix 8)
The metal element contained in the metal cation source includes any one or a combination of two or more of Mn, Fe, Co, Ni, Cu, Zn, Au, Pd, Pt, and In, preferably the metal Cation source is ferric chloride, ferrous chloride, ferric sulfate, ferrous sulfate, iron nitrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate , copper sulfate, copper acetate, copper nitrate, cupric chloride, cuprous chloride, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide , gold oxide, palladium acetate, palladium nitrate, palladium chloride, chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, indium acetate, and indium chloride. The preparation method according to Supplementary Note 1.
（付記９）
付記１～８のいずれか１項に記載の調整方法によって調製された合金化蛍光量子ドットであって、
蛍光発光ピーク波長が５００～１７００ｎｍ、好ましくは８００～１３５０ｎｍにあり、前記合金化蛍光量子ドットの絶対量子効率が８５％を超え、好ましくは、前記合金化蛍光量子ドットはＡｇＡｕＳｅ、ＡｇＡｕＳ、ＡｇＡｕＴｅ、ＣｕＡｇＳ、ＣｕＡｇＳｅ、ＡｇＩｎＴｅ２のいずれか１つまたは２つ以上の組み合わせを含み、
好ましくは、前記合金化蛍光量子ドットはドープされた合金化蛍光量子ドットを含み、好ましくはマンガンドープされたセレン化銀蛍光量子ドット、ニッケルドープされたテルル化銀蛍光量子ドット、インジウムドープされた硫化銀蛍光量子ドット、コバルトドープされた硫化銀蛍光量子ドットのいずれか１つまたは２つ以上の組み合わせを含み、
好ましくは、前記合金化蛍光量子ドットはコアシェル構造を有し、特に好ましくは、前記合金化蛍光量子ドットはＡｇ２Ｓ＠ＺｎＳ、Ａｇ２Ｔｅ＠Ａｇ２Ｓ、Ａｇ２Ｔｅ＠Ａｇ２Ｓｅ、Ａｇ２Ｓｅ＠Ａｇ２Ｓ、Ａｇ２Ｓｅ＠Ａｇ２Ｔｅ、Ａｇ２Ｓ＠Ａｇ２Ｓｅ、Ａｇ２Ｓ＠Ａｇ２Ｔｅ、Ａｇ２Ｓｅ＠ＺｎＳ、Ａｇ２Ｓｅ＠ＺｎＳｅ、Ａｇ２Ｓ＠ＭｎＳのいずれか１つまたは２つ以上の組み合わせを含む、合金化蛍光量子ドット。
(Appendix 9)
An alloyed fluorescent quantum dot prepared by the preparation method according to any one of Appendices 1 to 8,
The fluorescent emission peak wavelength is between 500 and 1700 nm, preferably between 800 and 1350 nm, the absolute quantum efficiency of the alloyed fluorescent quantum dots is over 85%, preferably the alloyed fluorescent quantum dots are AgAuSe, AgAuS, AgAuTe, CuAgS , CuAgSe, AgInTe 2 or a combination of two or more,
Preferably, said alloyed fluorescent quantum dots comprise doped alloyed fluorescent quantum dots, preferably manganese doped silver selenide fluorescent quantum dots, nickel doped silver telluride fluorescent quantum dots, indium doped sulfide any one or a combination of two or more of silver fluorescent quantum dots, cobalt-doped silver sulfide fluorescent quantum dots,
Preferably, said alloyed fluorescent quantum dots have a core-shell structure, particularly preferably said alloyed fluorescent quantum dots are Ag2S @ZnS, Ag2Te @ Ag2S , Ag2Te @ Ag2Se , Ag 2 Se@Ag 2 S, Ag 2 Se@Ag 2 Te, Ag 2 S@Ag 2 Se, Ag 2 S@Ag 2 Te, Ag 2 Se@ZnS, Ag 2 Se@ZnSe, Ag 2 S@MnS or alloyed fluorescent quantum dots, including one or a combination of two or more.
（付記１０）
銀源、セレン源、弱極性溶媒を含む第３の均一混合反応体系を溶媒熱反応させて、セレン化銀量子ドット前駆体を調製するステップと、
セレン化銀量子ドット前駆体、金源を含む第４の均一混合反応体系を０～２００℃で１０～７２時間陽イオン交換反応させ、近赤外線銀金セレン蛍光量子ドットを取得するステップと、を含むことを特徴とする近赤外線銀金セレン蛍光量子ドットの調製方法。
(Appendix 10)
Solvothermally reacting a third homogeneous mixed reaction system comprising a silver source, a selenium source, and a weakly polar solvent to prepare a silver selenide quantum dot precursor;
a fourth homogeneous mixed reaction system containing a silver selenide quantum dot precursor and a gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots; A method for preparing near-infrared silver-gold-selenium fluorescent quantum dots, comprising:
（付記１１）
まず銀源と弱極性溶媒を均一に混合し、次にセレン源を加えて、前記第３の均一混合反応体系を形成し、前記第３の均一混合反応体系を１００～３００℃で０．５～２４時間、好ましくは１～６時間溶媒熱反応させて、前記セレン化銀量子ドット前駆体を調製するステップを含み、
かつ／または、前記銀源とセレン源の質量比は１～１０：１～１０である、ことを特徴とする付記１０に記載の調製方法。
(Appendix 11)
First, a silver source and a weakly polar solvent are uniformly mixed, then a selenium source is added to form the third homogeneous mixed reaction system, and the third homogeneous mixed reaction system is heated at 100-300° C. to 0.5 solvent thermal reaction for ~24 hours, preferably 1-6 hours to prepare said silver selenide quantum dot precursor;
and/or the weight ratio of the silver source and the selenium source is 1-10:1-10.
（付記１２）
セレン化銀量子ドット前駆体、金源と弱極性溶媒を均一に混合して、前記第４の均一混合反応体系を形成するステップを含み、
かつ／または、前記セレン化銀量子ドット前駆体と金源の質量比は１～１０：１～１０である、ことを特徴とする付記１０に記載の調製方法。
(Appendix 12)
uniformly mixing a silver selenide quantum dot precursor, a gold source, and a weakly polar solvent to form the fourth homogeneously mixed reaction system;
and/or, the weight ratio of the silver selenide quantum dot precursor and the gold source is 1-10:1-10.
（付記１３）
前記銀塩は塩化銀、臭化銀、ヨウ化銀、硫酸銀、硝酸銀、炭酸銀、硫化銀、トリフルオロ酢酸銀、ジエチルジチオカルバミン酸銀のいずれか１つまたは２つ以上の組み合わせを含み、
かつ／または、前記セレン源は二酸化セレン、セレン粉末、セレン酸ナトリウム、亜セレン酸ナトリウム、セレン化ナトリウム、ジフェニルジセレニドのいずれか１つまたは２つ以上の組み合わせを含み、
かつ／または、前記弱極性溶媒はオレイルアミン、オレイン酸、オクタデセン、オクタデシルアミン、ドデシルアミン、テトラデシルアミン、ドデカンチオール、オクタンチオ、オクタデカンチオールのいずれか１つまたは２つ以上の組み合わせを含み、
かつ／または、前記金源はクロロ金酸ナトリウム、クロロ金酸、硝酸金、塩化金、水酸化金、酸化金、金ナノロッド、金粒子のいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする付記１０に記載の調製方法。
(Appendix 13)
The silver salt includes any one or a combination of two or more of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate, and silver diethyldithiocarbamate,
and/or the selenium source comprises any one or a combination of two or more of selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide, diphenyldiselenide,
and/or the weakly polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethio, and octadecanethiol,
and/or that the gold source comprises any one or a combination of two or more of sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods, and gold particles. The preparation method according to appendix 10, characterized in that
（付記１４）
付記１０～１３のいずれか１つに記載の方法によって調製された近赤外線銀金セレン蛍光量子ドットであって、前記近赤外線銀金セレン蛍光量子ドットの直径は２～２０ｎｍであり、サイズ分布が均一であり、その蛍光発光ピーク波長が８００～１７００ｎｍ、好ましくは８００～１３５０ｎｍであり、絶対蛍光量子収率が９０％を超える、近赤外線銀金セレン蛍光量子ドット。
(Appendix 14)
A near-infrared silver-gold-selenium fluorescent quantum dot prepared by the method according to any one of Appendices 10 to 13, wherein the near-infrared silver-gold-selenium fluorescent quantum dot has a diameter of 2-20 nm and a size distribution of A near-infrared silver gold selenium fluorescent quantum dot that is homogeneous, has a fluorescence emission peak wavelength of 800-1700 nm, preferably 800-1350 nm, and has an absolute fluorescence quantum yield of more than 90%.
（付記１５）
生物学的画像化、生物医学または近赤外線デバイス分野における付記９に記載の合金化蛍光量子ドットまたは付記１４に記載の近赤外線銀金セレン蛍光量子ドットの用途であって、好ましくは、前記近赤外線デバイスは近赤外線発光ダイオード、太陽電池、光検出器またはレーザーを含む、合金化蛍光量子ドットまたは近赤外線銀金セレン蛍光量子ドットの用途。
(Appendix 15)
Use of the alloyed fluorescent quantum dots according to
Claims (15)
銀系量子ドット前駆体、陰イオン源および／または金属陽イオン源を含む第２の均一混合反応体系を０～２６０℃で０．４～７２時間イオン交換反応させて、合金化蛍光量子ドットを取得するステップと、を含むことを特徴とする合金化蛍光量子ドットの調製方法。 solvothermally reacting a first homogeneous mixed reaction system comprising a silver source, an anion source, and a weakly polar solvent to prepare a silver-based quantum dot precursor;
A second homogeneous mixed reaction system comprising a silver-based quantum dot precursor, an anion source and/or a metal cation source is subjected to an ion exchange reaction at 0-260° C. for 0.4-72 hours to form alloyed fluorescent quantum dots. A method for preparing alloyed fluorescent quantum dots, comprising: obtaining.
蛍光発光ピーク波長が５００～１７００ｎｍ、好ましくは８００～１３５０ｎｍにあり、前記合金化蛍光量子ドットの絶対量子効率が８５％を超え、好ましくは、前記合金化蛍光量子ドットはＡｇＡｕＳｅ、ＡｇＡｕＳ、ＡｇＡｕＴｅ、ＣｕＡｇＳ、ＣｕＡｇＳｅ、ＡｇＩｎＴｅ２のいずれか１つまたは２つ以上の組み合わせを含み、
好ましくは、前記合金化蛍光量子ドットはドープされた合金化蛍光量子ドットを含み、好ましくはマンガンドープされたセレン化銀蛍光量子ドット、ニッケルドープされたテルル化銀蛍光量子ドット、インジウムドープされた硫化銀蛍光量子ドット、コバルトドープされた硫化銀蛍光量子ドットのいずれか１つまたは２つ以上の組み合わせを含み、
好ましくは、前記合金化蛍光量子ドットはコアシェル構造を有し、特に好ましくは、前記合金化蛍光量子ドットはＡｇ２Ｓ＠ＺｎＳ、Ａｇ２Ｔｅ＠Ａｇ２Ｓ、Ａｇ２Ｔｅ＠Ａｇ２Ｓｅ、Ａｇ２Ｓｅ＠Ａｇ２Ｓ、Ａｇ２Ｓｅ＠Ａｇ２Ｔｅ、Ａｇ２Ｓ＠Ａｇ２Ｓｅ、Ａｇ２Ｓ＠Ａｇ２Ｔｅ、Ａｇ２Ｓｅ＠ＺｎＳ、Ａｇ２Ｓｅ＠ＺｎＳｅ、Ａｇ２Ｓ＠ＭｎＳのいずれか１つまたは２つ以上の組み合わせを含む、合金化蛍光量子ドット。 An alloyed fluorescent quantum dot prepared by the preparation method according to any one of claims 1 to 8,
The fluorescent emission peak wavelength is between 500 and 1700 nm, preferably between 800 and 1350 nm, the absolute quantum efficiency of the alloyed fluorescent quantum dots is over 85%, preferably the alloyed fluorescent quantum dots are AgAuSe, AgAuS, AgAuTe, CuAgS , CuAgSe, AgInTe 2 or a combination of two or more,
Preferably, said alloyed fluorescent quantum dots comprise doped alloyed fluorescent quantum dots, preferably manganese doped silver selenide fluorescent quantum dots, nickel doped silver telluride fluorescent quantum dots, indium doped sulfide any one or a combination of two or more of silver fluorescent quantum dots, cobalt-doped silver sulfide fluorescent quantum dots,
Preferably, said alloyed fluorescent quantum dots have a core-shell structure, particularly preferably said alloyed fluorescent quantum dots are Ag2S @ZnS, Ag2Te @ Ag2S , Ag2Te @ Ag2Se , Ag 2 Se@Ag 2 S, Ag 2 Se@Ag 2 Te, Ag 2 S@Ag 2 Se, Ag 2 S@Ag 2 Te, Ag 2 Se@ZnS, Ag 2 Se@ZnSe, Ag 2 S@MnS or alloyed fluorescent quantum dots, including one or a combination of two or more.
セレン化銀量子ドット前駆体、金源を含む第４の均一混合反応体系を０～２００℃で１０～７２時間陽イオン交換反応させ、近赤外線銀金セレン蛍光量子ドットを取得するステップと、を含むことを特徴とする近赤外線銀金セレン蛍光量子ドットの調製方法。 Solvothermally reacting a third homogeneous mixed reaction system comprising a silver source, a selenium source, and a weakly polar solvent to prepare a silver selenide quantum dot precursor;
a fourth homogeneous mixed reaction system containing a silver selenide quantum dot precursor and a gold source is subjected to a cation exchange reaction at 0-200° C. for 10-72 hours to obtain near-infrared silver-gold-selenium fluorescent quantum dots; A method for preparing near-infrared silver-gold-selenium fluorescent quantum dots, comprising:
かつ／または、前記銀源とセレン源の質量比は１～１０：１～１０である、ことを特徴とする請求項１０に記載の調製方法。 First, a silver source and a weakly polar solvent are uniformly mixed, then a selenium source is added to form the third homogeneous mixed reaction system, and the third homogeneous mixed reaction system is heated at 100-300° C. to 0.5 solvent thermal reaction for ~24 hours, preferably 1-6 hours to prepare said silver selenide quantum dot precursor;
and/or the weight ratio of the silver source and the selenium source is 1-10:1-10.
かつ／または、前記セレン化銀量子ドット前駆体と金源の質量比は１～１０：１～１０である、ことを特徴とする請求項１０に記載の調製方法。 uniformly mixing a silver selenide quantum dot precursor, a gold source, and a weakly polar solvent to form the fourth homogeneously mixed reaction system;
and/or the weight ratio of the silver selenide quantum dot precursor and the gold source is 1-10:1-10.
かつ／または、前記セレン源は二酸化セレン、セレン粉末、セレン酸ナトリウム、亜セレン酸ナトリウム、セレン化ナトリウム、ジフェニルジセレニドのいずれか１つまたは２つ以上の組み合わせを含み、
かつ／または、前記弱極性溶媒はオレイルアミン、オレイン酸、オクタデセン、オクタデシルアミン、ドデシルアミン、テトラデシルアミン、ドデカンチオール、オクタンチオ、オクタデカンチオールのいずれか１つまたは２つ以上の組み合わせを含み、
かつ／または、前記金源はクロロ金酸ナトリウム、クロロ金酸、硝酸金、塩化金、水酸化金、酸化金、金ナノロッド、金粒子のいずれか１つまたは２つ以上の組み合わせを含む、ことを特徴とする請求項１０に記載の調製方法。 The silver salt includes any one or a combination of two or more of silver chloride, silver bromide, silver iodide, silver sulfate, silver nitrate, silver carbonate, silver sulfide, silver trifluoroacetate, and silver diethyldithiocarbamate,
and/or the selenium source comprises any one or a combination of two or more of selenium dioxide, selenium powder, sodium selenate, sodium selenite, sodium selenide, diphenyldiselenide,
and/or the weakly polar solvent includes any one or a combination of two or more of oleylamine, oleic acid, octadecene, octadecylamine, dodecylamine, tetradecylamine, dodecanethiol, octanethio, and octadecanethiol,
and/or that the gold source comprises any one or a combination of two or more of sodium chloroaurate, chloroauric acid, gold nitrate, gold chloride, gold hydroxide, gold oxide, gold nanorods, and gold particles. The preparation method according to claim 10, characterized in that
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